CN115850044A - Synthetic method of p-methoxybenzaldehyde - Google Patents
Synthetic method of p-methoxybenzaldehyde Download PDFInfo
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- CN115850044A CN115850044A CN202211636906.3A CN202211636906A CN115850044A CN 115850044 A CN115850044 A CN 115850044A CN 202211636906 A CN202211636906 A CN 202211636906A CN 115850044 A CN115850044 A CN 115850044A
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- molecular sieve
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- methoxybenzaldehyde
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- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002808 molecular sieve Substances 0.000 claims abstract description 78
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010306 acid treatment Methods 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 22
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 20
- 238000007069 methylation reaction Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 238000001308 synthesis method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 230000002194 synthesizing effect Effects 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 235000010338 boric acid Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 229910001952 rubidium oxide Inorganic materials 0.000 claims description 2
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 40
- 239000000243 solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005303 weighing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000009917 Crataegus X brevipes Nutrition 0.000 description 1
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 description 1
- 235000009685 Crataegus X maligna Nutrition 0.000 description 1
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 description 1
- 235000009486 Crataegus bullatus Nutrition 0.000 description 1
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 description 1
- 235000009682 Crataegus limnophila Nutrition 0.000 description 1
- 235000004423 Crataegus monogyna Nutrition 0.000 description 1
- 240000000171 Crataegus monogyna Species 0.000 description 1
- 235000002313 Crataegus paludosa Nutrition 0.000 description 1
- 235000009840 Crataegus x incaedua Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940124623 antihistamine drug Drugs 0.000 description 1
- 239000000739 antihistaminic agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
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Abstract
The invention discloses a synthetic method of p-methoxybenzaldehyde. According to the synthesis method, p-hydroxybenzaldehyde and dimethyl carbonate are taken as raw materials, methylation reaction is carried out in the presence of a catalyst to generate the p-methoxybenzaldehyde, and the catalyst is a supported catalyst and comprises a carrier and a metal oxide supported on the carrier; the carrier is a mesoporous molecular sieve and contains mesopores, and the aperture of each mesopore is 2-50nm. The mesoporous molecular sieve can be prepared from one or more of ZSM-5 molecular sieve, Y-type molecular sieve, beta molecular sieve, MCM-41 molecular sieve and SBA-15 molecular sieve by sequentially carrying out acid treatment and alkali treatment on the molecular sieve. According to the invention, the molecular sieve with the mesoporous structure is used as the catalyst carrier, so that the reaction selectivity of the methylation reaction and the yield of the target product can be improved, and the synthetic method is environment-friendly.
Description
Technical Field
The invention relates to a synthetic method of p-methoxybenzaldehyde.
Background
P-methoxybenzaldehyde is one of important spices with hawthorn flower fragrance, is colorless or light yellow liquid, and is widely used in the formula of daily chemical essence and edible essence; meanwhile, the derivative is also an important medical intermediate, and can be used for synthesizing porphyrin photosensitizer and antihistamine drug intermediate.
The p-methoxybenzaldehyde and dimethyl sulfate are mostly adopted as raw materials to synthesize the p-methoxybenzaldehyde industrially, the yield of the method is high, but the toxicity and the corrosivity of the dimethyl sulfate are high, the problems of industrial three wastes exist, and the environmental protection treatment cost is high.
In the prior art, p-methoxybenzaldehyde and dimethyl carbonate are also used as raw materials to synthesize p-methoxybenzaldehyde, for example, chinese patent publication No. CN106946674a discloses that p-methoxybenzaldehyde and dimethyl carbonate are used as raw materials, at a temperature range of 130-180 ℃, polar solvent water is used as a solvent, basic substance Y-type zeolite is used as a catalyst, and a proper surfactant turkish red oil is added as an emulsifier to prepare p-methoxybenzaldehyde. Chinese laid-open patent CN104628545a discloses synthesis of p-methoxybenzaldehyde from p-methoxybenzaldehyde and dimethyl carbonate as raw materials in the presence of a catalyst composition of a first catalyst phase transfer catalyst and a second catalyst such as a basic catalyst, the reaction system also uses an organic solvent, and the yield is not high enough.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a synthetic method of p-methoxybenzaldehyde, which does not need solvent and emulsifier, has environment-friendly process, high yield of target products and high reaction selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a synthetic method of p-methoxybenzaldehyde takes p-hydroxybenzaldehyde and dimethyl carbonate as raw materials, methylation reaction is carried out in the presence of a catalyst to generate the p-methoxybenzaldehyde, and the catalyst is a supported catalyst and comprises a carrier and metal oxide loaded on the carrier; the carrier is a mesoporous molecular sieve and contains mesopores, and the aperture of each mesopore is 2-50nm.
In some embodiments, the mesoporous molecular sieve is selected from the group consisting of one or more combinations of ZSM-5 molecular sieves, Y-type molecular sieves, beta molecular sieves, MCM-41 molecular sieves, and SBA-15 molecular sieves.
Preferably, the mesoporous molecular sieve is a Y-type molecular sieve.
In some embodiments, the mesoporous molecular sieve is prepared by sequentially subjecting a molecular sieve to acid treatment and base treatment. During acid treatment, the molecular sieve framework is subjected to dealumination reaction, and simultaneously alumina in a non-framework is removed; when in alkali treatment, the framework of the molecular sieve has desilication reaction. After acid treatment and alkali treatment are carried out in sequence, the molecular sieve forms a mesoporous structure.
In some embodiments, the molecular sieve has a silica to alumina molar ratio of 3 to 500:1.
in some embodiments, the mesoporous molecular sieve is prepared by a process comprising: 1) Carrying out acid treatment on the molecular sieve by using an acid solution, and washing, drying and roasting to obtain the acid-treated molecular sieve; 2) And (3) carrying out alkali treatment on the molecular sieve subjected to acid treatment by adopting an alkali solution, and washing, drying and roasting to obtain the mesoporous molecular sieve.
In some embodiments, in step 1), the acid in the acid solution is selected from a combination of one or more of oxalic acid, boric acid, acetic acid, hydrochloric acid, and propionic acid.
Preferably, the acid in the acid solution is boric acid.
In some embodiments, in step 2), the base in the base solution is selected from a combination of one or more of sodium hydroxide, sodium carbonate, organic amine, and organic quaternary ammonium base.
Preferably, the base in the base solution is sodium hydroxide.
In some embodiments, the organic amine is selected from the group consisting of one or more combinations of ethylenediamine, triethylamine, n-butylamine, and piperidine.
In some embodiments, the organic quaternary ammonium base is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
In some embodiments, in step 1), the molar concentration of the acid solution is 0.05 to 5moL/L.
Preferably, in the step 1), the molar concentration of the acid solution is 0.05-2moL/L.
In some embodiments, the temperature of the acid treatment in step 1) is 30 to 180 ℃.
Preferably, in step 1), the temperature of the acid treatment is 30 to 120 ℃.
In some embodiments, in step 1), the acid treatment time is 0.5 to 48 hours.
Preferably, in the step 1), the acid treatment time is 0.5 to 24 hours.
In some embodiments, in step 2), the molar concentration of the base solution is 0.05 to 5moL/L.
Preferably, in the step 2), the molar concentration of the alkali solution is 0.05-2moL/L.
In some embodiments, the temperature of the alkali treatment in step 2) is 30 to 180 ℃.
Preferably, in the step 2), the temperature of the alkali treatment is 30 to 120 ℃.
In some embodiments, in step 2), the time for the alkali treatment is 0.5 to 48 hours.
Preferably, in the step 2), the time of the alkali treatment is 0.5 to 24 hours.
In some embodiments, the catalyst is prepared by a process comprising the steps of: and carrying out ball milling and roasting on the active metal salt and the mesoporous molecular sieve to obtain the catalyst.
In some embodiments, the active metal salt is selected from the group consisting of metal oxide corresponding nitrate, acetate and acetylacetone salts in one or more combinations.
In some embodiments, the temperature of the ball milling is 30 to 100 ℃.
In some embodiments, the ball milling time is 0.5 to 48 hours.
In some embodiments, the temperature of the firing is 300 to 600 ℃.
In some embodiments, the calcination is for a time period of 0.5 to 12 hours.
In some embodiments, the metal oxide is selected from the group consisting of zinc oxide, manganese oxide, magnesium oxide, barium oxide, calcium oxide, lithium oxide, sodium oxide, potassium oxide, and rubidium oxide.
Preferably, the metal oxide is magnesium oxide.
In some embodiments, the mass of the metal oxide is 3% to 30% of the mass of the catalyst.
In some embodiments, the temperature of the methylation reaction is from 80 to 250 ℃.
In some embodiments, the pressure of the methylation reaction is from 0.3 to 6MPa.
In some embodiments, the synthesis method comprises the steps of: 1) Mixing the p-hydroxybenzaldehyde, the dimethyl carbonate and a catalyst to obtain a reaction mixture; 2) And carrying out methylation reaction on the reaction mixture under an inert atmosphere to obtain the p-methoxybenzaldehyde. The synthesis method is a batch method.
In some embodiments, the mass ratio of the catalyst to the p-hydroxybenzaldehyde is 0.01 to 0.2:1.
in some embodiments, the molar ratio of the dimethyl carbonate to the p-hydroxybenzaldehyde is from 1 to 10:1.
in some embodiments, the synthesis method comprises the steps of: 1) Filling the catalyst in a fixed bed reactor, and introducing inert gas into the fixed bed reactor to ensure that the pressure in the fixed bed reactor reaches the reaction pressure; 2) And heating the fixed bed reactor to a reaction temperature, and continuously introducing the p-hydroxybenzaldehyde and the dimethyl carbonate into the fixed bed reactor to perform methylation reaction to obtain the methoxybenzaldehyde. The synthesis method is a continuous method.
In some embodiments, the molar ratio of the dimethyl carbonate to the p-hydroxybenzaldehyde is from 1 to 10:1.
in some embodiments, the mass space velocity of the p-hydroxybenzaldehyde is 0.2-10h -1 。
The invention also provides the catalyst. The carrier of the catalyst is of a mesoporous structure, and when the catalyst is used for methylation reaction of p-hydroxybenzaldehyde, the selectivity of the reaction and the product yield can be improved.
Compared with the prior art, the invention has the following advantages:
the synthetic method of the invention uses the green and environment-friendly dimethyl carbonate, compared with the traditional dimethyl sulfate, the process is more environment-friendly, and the process cost is further reduced; the synthetic method of the invention does not need to use solvent and emulsifier, thus further improving the environmental protection degree; in addition, the synthesis method adopts the mesoporous molecular sieve with the mesoporous structure as the catalyst carrier, the carrier has larger pore channels, compared with the microporous structure of the conventional carrier, the carrier can obviously improve the mass transfer efficiency of a reaction system, obviously improve the selectivity of methylation reaction and obviously improve the yield of the target product p-methoxybenzaldehyde. By adopting the synthesis method, the conversion rate of the p-hydroxybenzaldehyde can reach 98%, and the selectivity of the p-methoxybenzaldehyde can reach 96%.
The carrier of the catalyst has a mesoporous structure, so that the mass transfer efficiency of the reaction can be improved, the reaction rate can be improved, and the reaction selectivity of the methylation reaction and the yield of the target product can be improved. Meanwhile, the catalyst has high stability, and the catalytic activity is basically unchanged after continuous catalytic reaction for 500 hours.
Drawings
FIG. 1 shows preparation example 1 of Y-type molecular sieve (untreated), supported metal catalyst Mg-NaOH-0.05-H 3 BO 3 X-ray diffraction spectrum of/Y;
FIG. 2 shows Mg-NaOH-0.05-H as the supported metal catalyst in preparation example 1 3 BO 3 A desorption isotherm of/Y;
FIG. 3 shows Mg-NaOH-0.05-H as the supported metal catalyst in preparation example 1 3 BO 3 The aperture distribution map of/Y;
FIG. 4 shows Mg-NaOH-0.05-H as the supported metal catalyst in preparation example 1 3 BO 3 Graph of 500h stability test results of/Y.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Preparation example 1
The preparation example provides a catalyst, and the preparation method specifically comprises the following steps:
1) Weighing 100.0g Y type molecular sieve (the X-ray diffraction spectrum is shown in figure 1, the molar ratio of silicon oxide to aluminum oxide is 3) and placing into a ceramic crucible, drying in a 120 ℃ oven for 5h, removing water, placing into a muffle furnace, and treating at 500 ℃ for 5h for later use. Then 20.0g of the above treated Y-type molecular sieve was accurately weighed and placed in a three-necked flask equipped with a reflux condenser and stirring, 100mL of a boric acid solution having a concentration of 0.05mol/L was added, sufficiently stirred and heated to 100 ℃ for treatment for 5 hours. Taking out the mixed solution, performing suction filtration, and washing with water until the pH value is approximately equal to 7; drying the filter cake in a 120 ℃ oven, and roasting in a 550 ℃ muffle furnace for 4H in the air atmosphere to obtain the acid-treated Y-type molecular sieve which is marked as 0.05-H 3 BO 3 Y (0.05 acid treatment concentration).
2) Adding 100mL of sodium hydroxide solution with the concentration of 0.10mol/L into the acid-treated Y-type molecular sieve, fully stirring, heating to 120 ℃, treating for 10 hours, taking out, carrying out suction filtration, and washing with water until the pH value is approximately equal to 7; the filter cake is placed in a 120 ℃ oven for drying and is roasted for 4 hours in a muffle furnace at 550 ℃ under the air atmosphere, and the mesoporous molecular sieve is obtained and is marked as NaOH-0.05-H 3 BO 3 /Y。
3) 18.54g of magnesium nitrate and the mesoporous molecular sieve NaOH-0.05-H are added into a ball mill 3 BO 3 Ball milling at 50 deg.c and 1000r/min for 4 hr, and roasting in a muffle furnace at 600 deg.c in air atmosphere for 10 hr to obtain Mg-NaOH-0.05-H 3 BO 3 a/Y supported catalyst.
FIG. 1, FIG. 2 and FIG. 3 are views of preparation example 1, respectively, showing Mg-NaOH-0.05-H as a supported metal catalyst 3 BO 3 The X-ray diffraction spectrogram, the adsorption and desorption isotherm and the particle size distribution diagram of the/Y; as can be seen from the comparison of the X-ray diffraction spectra of FIG. 1, the crystal structure of the Y-type molecular sieve is not changed significantly after the treatment and the loading; as shown in FIG. 2, mg-NaOH-0.05-H 3 BO 3 The hysteresis loop of the/Y catalyst is obvious in adsorption and desorption isotherm, which indicates that Mg-NaOH-0.05-H 3 BO 3 the/Y catalyst has an obvious mesoporous structure; as can be seen from FIG. 3, mg-NaOH-0.05-H 3 BO 3 The catalyst/Y has obvious mesoporous structure.
Preparation example 2
This preparation provides a number of catalysts, which are prepared in essentially the same manner as in preparation 1, except that: the Y-type molecular sieve in the step 1) is respectively replaced by other carriers of ZSM-5 (the molar ratio of silicon oxide to aluminum oxide is 45), beta (the molar ratio of silicon oxide to aluminum oxide is 25), MCM-41 (the molar ratio of silicon oxide to aluminum oxide is 30) and SBA-15 (the molar ratio of silicon oxide to aluminum oxide is 400). The finally prepared supported catalyst is respectively marked as Mg-NaOH-0.05-H 3 BO 3 /ZSM-5、Mg-NaOH-0.05-H 3 BO 3 /Beta、Mg-NaOH-0.05-H 3 BO 3 /MCM-41、Mg-NaOH-0.05-H 3 BO 3 /SBA-15。
Preparation example 3
This preparation provides a number of catalysts, which are prepared in essentially the same manner as in preparation 1, except that: replacing the boric acid in the step 1) with oxalic acid, acetic acid, hydrochloric acid and propionic acid respectively. The finally prepared supported catalyst is respectively marked as Mg-NaOH-0.05-C 2 H 2 O 4 //Y、Mg-NaOH-0.05-CH 3 COOH/Y、Mg-NaOH-0.05-HCl/Y、Mg-NaOH-0.05-CH 3 CH 2 COOH/Y。
Preparation example 4
This preparation provides a number of catalysts, which are prepared in essentially the same manner as in preparation 1, except that: replacing sodium hydroxide in the step 2) with sodium carbonate, ethylenediamine (EDA) and triethylamine (Et) respectively 3 N), tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH). The finally prepared supported catalyst is respectively marked as Mg-Na 2 CO 3 -0.05-H 3 BO 3 /Y、Mg-EDA-0.05-H 3 BO 3 /Y、Mg-Et 3 N-0.05-H 3 BO 3 /Y、Mg-TMAH-0.05-H 3 BO 3 /Y、Mg-TEAH-0.05-H 3 BO 3 /Y、Mg-TPAH-0.05-H 3 BO 3 /Y、Mg-TBAH-0.05-H 3 BO 3 /Y。
Preparation example 5
This preparation provides a number of catalysts, which are prepared in essentially the same manner as in preparation 1, except that: replacing the magnesium nitrate in the step 3) with potassium nitrate, barium nitrate, copper nitrate, ferric nitrate, silver nitrate, calcium nitrate and cobalt nitrate respectively. The finally prepared supported catalyst is respectively marked as K-NaOH-0.05-H 3 BO 3 /Y、Ba-NaOH-0.05-H 3 BO 3 /Y、Cu-NaOH-0.05-H 3 BO 3 /Y、Fe-NaOH-0.05-H 3 BO 3 /Y、Ag-NaOH-0.05-H 3 BO 3 /Y、Ca-NaOH-0.05-H 3 BO 3 /Y、Co-NaOH-0.05-H 3 BO 3 /Y。
Preparation example 6
The preparation example provides a catalyst, and the preparation method specifically comprises the following steps:
1) Weighing 100.0g of MCM-41 type molecular sieve, putting the molecular sieve into a ceramic crucible, drying the molecular sieve in a 120 ℃ oven for 5 hours, removing water, putting the molecular sieve into a muffle furnace, and treating the molecular sieve at 500 ℃ for 5 hours for later use. Then 20.0g of the above-treated MCM-41 type molecular sieve was accurately weighed and placed in a three-necked flask equipped with a reflux condenser and stirring, 100mL of an acetic acid solution with a concentration of 0.10mol/L was added, and the mixture was sufficiently stirred and heated to 100 ℃ to be treated for 5 hours. Taking out the mixed solution, performing suction filtration, and washing with water until the pH value is approximately equal to 7; drying the filter cake in a 120 ℃ drying oven, and roasting for 4 hours in a 550 ℃ muffle furnace in the air atmosphere to obtain the acid-treated MCM-41 type molecular sieve which is marked as 0.10-CH 3 COOH/MCM-41 (0.10 at acid treatment concentration).
2) Adding 100mL of ethylenediamine solution with the concentration of 0.30mol/L into the MCM-41 type molecular sieve subjected to acid treatment, fully stirring, heating to 120 ℃, treating for 10 hours, taking out, performing suction filtration, and washing with water until the pH value is approximately equal to 7; putting the filter cake into a 120 ℃ drying oven for drying and roasting in a 550 ℃ muffle furnace for 4 hours in the air atmosphere to obtain the mesoporous molecular sieve, which is recorded as EDA-0.10-CH 3 COOH/MCM-41。
3) 18.54g of magnesium nitrate and the mesoporous molecular sieve EDA-0.10-CH are added into a ball mill 3 Ball milling COOH/MCM-41 at 50 deg.c and 1000r/min for 6 hr in air atmosphereRoasting in a muffle furnace at 600 ℃ for 10h to obtain Mg-EDA-0.10-CH 3 COOH/MCM-41 supported catalyst.
Comparative preparation example 1
The comparative preparation example provides a catalyst, and the preparation method thereof specifically comprises the following steps:
1) Weighing 100.0g Y type molecular sieve, placing into a porcelain crucible, drying in a 120 ℃ oven for 5h, removing water, placing into a muffle furnace, and processing at 500 ℃ for 5h for later use.
2) Then accurately weighing 20.0g of the Y-type molecular sieve which is not treated by acid and alkali, directly neutralizing 18.54g of magnesium nitrate in a ball mill for ball milling, wherein the ball milling temperature is 50 ℃, the rotating speed is 1000r/min, the grinding time is 4h, and then roasting in a muffle furnace at 600 ℃ in an air atmosphere for 10h to obtain the Mg-Y catalyst.
Comparative preparation example 2
The comparative preparation example provides a catalyst, and the preparation method thereof specifically comprises the following steps:
1) Weighing 100.0g of ZSM-5 molecular sieve, putting the ZSM-5 molecular sieve into a ceramic crucible, drying the molecular sieve in a 120 ℃ oven for 5 hours, removing water, putting the molecular sieve into a muffle furnace, and treating the molecular sieve at 500 ℃ for 5 hours for later use.
2) Then accurately weighing 20.0g of the ZSM-5 molecular sieve which is not treated by acid and alkali, directly neutralizing 18.54g of magnesium nitrate in a ball mill for ball milling at the ball milling temperature of 50 ℃, the rotating speed of 1000r/min and the grinding time of 4h, and then roasting in a muffle furnace at the temperature of 600 ℃ in the air atmosphere for 10h to obtain the Mg-ZSM-5 catalyst.
Comparative preparation example 3
This comparative preparation provides a catalyst which is prepared in essentially the same manner as preparation 1, except that: the alkali treatment in the step 2) is not carried out, and the specific steps are as follows:
1) Weighing 100.0g Y type molecular sieve (X-ray diffraction spectrum is shown in figure 1), placing into a porcelain crucible, drying in a 120 deg.C oven for 5h, removing water, placing into a muffle furnace, and processing at 500 deg.C for 5h. Then 20.0g of the above treated Y-type molecular sieve was accurately weighed and placed in a three-necked flask equipped with a reflux condenser tube and stirring, 100mL of a boric acid solution having a concentration of 0.05mol/L was added, and the mixture was sufficiently stirred and heated to 100 deg.CThe treatment is carried out for 5h. Taking out the mixed solution, performing suction filtration, and washing with water until the pH value is approximately equal to 7; drying the filter cake in a 120 ℃ oven, and roasting in a 550 ℃ muffle furnace for 4H in the air atmosphere to obtain the acid-treated Y-type molecular sieve which is marked as 0.05-H 3 BO 3 Y (0.05 acid treatment concentration).
2) 18.54g of magnesium nitrate and the above-mentioned 0.05-H were added to the ball mill 3 BO 3 Performing ball milling on the powder/Y at the ball milling temperature of 50 ℃, the rotation speed of 1000r/min and the grinding time of 4H, and then roasting the powder in a muffle furnace at the temperature of 600 ℃ in the air atmosphere for 10H to obtain Mg-0.05-H 3 BO 3 a/Y supported catalyst.
Comparative preparation example 4
This comparative preparation provides a catalyst which is prepared in essentially the same manner as preparation 1, except that: the acid treatment in step 2) is not carried out, and the specific steps are as follows:
1) Weighing 100.0g Y type molecular sieve, placing into a porcelain crucible, drying in a 120 ℃ oven for 5h, removing water, placing into a muffle furnace, and processing at 500 ℃ for 5h for later use.
2) Adding 100mL of sodium hydroxide solution with the concentration of 0.10mol/L into the Y-type molecular sieve, fully stirring, heating to 120 ℃, treating for 10 hours, taking out, filtering, and washing with water until the pH value is approximately equal to 7; and (3) drying the filter cake in a 120 ℃ drying oven and roasting for 4 hours in a 550 ℃ muffle furnace in the air atmosphere to obtain the mesoporous molecular sieve, and recording as NaOH/Y.
3) Adding 18.54g of magnesium nitrate and the NaOH/Y into a ball mill for ball milling, wherein the ball milling temperature is 50 ℃, the rotating speed is 1000r/min, the grinding time is 4h, and then roasting in a muffle furnace at 600 ℃ for 10h in an air atmosphere to obtain the Mg-NaOH/Y supported catalyst.
Example 1
The performance of the supported catalysts prepared in production examples 1 to 5 and comparative production examples 1 to 4 was examined using a fixed bed reactor (stainless steel tube) having an outer diameter of 18mm, an inner diameter of 12mm, a length of 450mm, and a catalyst loading of 10g. The reaction conditions are 200g of p-hydroxybenzaldehyde, 590.1g of dimethyl carbonate and 3h of mass space velocity of the p-hydroxybenzaldehyde -1 The reaction temperature is 150 ℃, and the reaction pressure is 2MPa. The reaction product passes through an oil-water separatorPerforming quantitative analysis by using Agilent 7890 gas chromatograph, wherein the chromatographic column is HP-INNOWax, and the detector is FID detector. Conversion and selectivity were calculated using normalization. The results are shown in tables 1-4 below.
Table 1: comparison of catalyst reactivity for different supports
As can be seen from Table 1, the effect of the catalysts corresponding to each support is significantly better than that of the catalysts of comparative preparation examples 1-2. And the catalyst using the Y-type molecular sieve as the carrier has the best catalytic effect.
Table 2: comparison of catalyst reactivity for different acid treatments
As can be seen from Table 2, the effect of the catalysts corresponding to the different acid treatments is significantly better than that of the catalyst of comparative preparation example 4. And the catalyst treated with boric acid has the best catalytic effect.
Table 3: comparison of catalyst reactivity for different base treatments
As can be seen from Table 3, the effect of the catalysts corresponding to the various alkali treatments is significantly better than that of the catalyst of comparative preparation example 3. And the catalytic effect of the corresponding catalyst treated with sodium hydroxide is the best.
Table 4: comparison of catalyst reactivity with different metals as active components
| Catalyst and process for preparing same | Conversion ratio of p-hydroxybenzaldehyde (%) | P-methoxybenzaldehyde selectivity (%) |
| Ba-NaOH-0.05-H 3 BO 3 /Y | 90.5 | 87.6 |
| Mg-NaOH-0.05-H 3 BO 3 /Y | 98.2 | 96.3 |
| Cu-NaOH-0.05-H 3 BO 3 /Y | 85.4 | 87.9 |
| Fe-NaOH-0.05-H 3 BO 3 /Y | 85.7 | 77.1 |
| Ca-NaOH-0.05-H 3 BO 3 /Y | 84.1 | 75.5 |
| Co-NaOH-0.05-H 3 BO 3 /Y | 81.1 | 79.2 |
| K-NaOH-0.05-H 3 BO 3 /Y | 82.5 | 75.1 |
| Ag-NaOH-0.05-H 3 BO 3 /Y | 71.2 | 75.3 |
As is clear from Table 4, the catalysts corresponding to the active components of the respective metal oxides are all excellent in effect, and the catalyst having magnesium oxide as the active component is the most excellent in catalytic effect.
Example 2
Mg-NaOH-0.05-H prepared in preparation example 1 was added to a fixed bed reactor (stainless steel tube) 3 BO 3 the/Y catalyst is used for investigating the reaction performance of synthesizing p-methoxybenzaldehyde, the outer diameter of the reactor is 18mm, the inner diameter of the reactor is 12mm, the length of the reactor is 450mm, the reaction product is subjected to quantitative analysis after passing through an oil-water separator, and an Agilent 7890 gas chromatograph is adopted for analysis, wherein a chromatographic column is HP-INNOWax, and a detector is a FID detector. Conversion and selectivity were calculated using normalization. The results are shown in tables 5 to 9 below.
The reaction conditions of table 5 were: mg-NaOH-0.05-H 3 BO 3 The dosage of the/Y load type catalyst is 10g, the dosage of the p-hydroxybenzaldehyde is 200g, and the molar ratio of the dosage of the dimethyl carbonate to the dosage of the p-hydroxybenzaldehyde is (1-10): 1, the mass airspeed of the parahydroxybenzaldehyde is 3h -1 The reaction temperature is 150 ℃, and the reaction pressure is 2MPa.
Table 5: effect of starting Material molar ratio on Synthesis
The reaction conditions of table 6 were: mg-NaOH-0.05-H 3 BO 3 The dosage of the/Y load type catalyst is 10g, the dosage of the p-hydroxybenzaldehyde is 200g, and the dimethyl carbonateThe material feeding amount is 590.1g, the mass space velocity of the p-hydroxybenzaldehyde is 3h -1 The reaction pressure is 2MPa.
Table 6: influence of reaction temperature on the Synthesis
| Reaction temperature | Conversion ratio of p-hydroxybenzaldehyde (%) | P-methoxybenzaldehyde selectivity (%) |
| 80 | 51.4 | 50.4 |
| 100 | 72.5 | 81.3 |
| 120 | 87.4 | 87.5 |
| 140 | 95.2 | 95.9 |
| 150 | 98.2 | 96.3 |
| 160 | 96.9 | 95.0 |
| 170 | 96.0 | 90.5 |
| 200 | 95.5 | 81.2 |
| 250 | 95.8 | 80.2 |
The reaction conditions of table 7 were: mg-NaOH-0.05-H 3 BO 3 The dosage of the/Y load type catalyst is 10g, the dosage of the p-hydroxybenzaldehyde is 200g, the dosage of the dimethyl carbonate is 590.1g, the mass airspeed of the p-hydroxybenzaldehyde is 0.2-10h -1 The reaction temperature is 150 ℃, and the reaction pressure is 2MPa.
Table 7: influence of mass airspeed of p-hydroxybenzaldehyde on synthesis
| Airspeed | Conversion ratio of p-hydroxybenzaldehyde (%) | P-methoxybenzaldehyde selectivity (%) |
| 0.2 | 80.7 | 87.9 |
| 1 | 88.1 | 86.1 |
| 2 | 85.4 | 87.5 |
| 2.5 | 90.3 | 95.1 |
| 3 | 98.2 | 96.3 |
| 3.5 | 95.2 | 95.2 |
| 4 | 94.5 | 95.2 |
| 6 | 90.3 | 89.4 |
| 8 | 88.8 | 88.1 |
| 10 | 85.6 | 88.1 |
The reaction conditions of table 8 are: mg-NaOH-0.05-H 3 BO 3 The dosage of the/Y load type catalyst is 10g, the dosage of the p-hydroxybenzaldehyde is 200g, the dosage of the dimethyl carbonate is 590.1g, and the mass airspeed of the p-hydroxybenzaldehyde is 3h -1 Reaction temperatureThe reaction pressure is 0.3-6MPa at 150 ℃.
Table 8: effect of reaction pressure on Synthesis
| Pressure of | Conversion ratio of p-hydroxybenzaldehyde (%) | P-methoxybenzaldehyde selectivity (%) |
| 0.3 | 55.1 | 57.1 |
| 1 | 68.6 | 86.3 |
| 1.5 | 88.4 | 92.1 |
| 2 | 98.2 | 96.3 |
| 2.5 | 94.3 | 95.1 |
| 3 | 93.3 | 95.2 |
| 4 | 92.8 | 94.9 |
| 5 | 90.9 | 94.4 |
| 6 | 85.1 | 92.1 |
The reaction conditions of table 9 were: mg-NaOH-0.05-H 3 BO 3 The mass ratio of the charging amount of the/Y load type catalyst to the charging amount of the p-hydroxybenzaldehyde is (0.01-0.2): 1, 200g of p-hydroxybenzaldehyde, 590.1g of dimethyl carbonate and 3h of mass space velocity of p-hydroxybenzaldehyde -1 The reaction temperature is 150 ℃, and the reaction pressure is 2MPa.
Table 9: influence of catalyst input on Synthesis
As shown in FIG. 4, in the 500-hour stability test, the p-hydroxybenzaldehyde group was substantially completely converted, and the selectivity to p-methoxybenzaldehyde was maintained at about 96%, indicating that Mg-NaOH-0.05-H prepared in preparation example 1 3 BO 3 the/Y supported catalyst has excellent reaction activity and stability.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (16)
1. A synthetic method of p-methoxybenzaldehyde takes p-hydroxybenzaldehyde and dimethyl carbonate as raw materials, and methylation reaction is carried out in the presence of a catalyst to generate the p-methoxybenzaldehyde, which is characterized in that: the catalyst is a supported catalyst and comprises a carrier and a metal oxide supported on the carrier; the carrier is a mesoporous molecular sieve and contains mesopores, and the aperture of each mesopore is 2-50nm.
2. The method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the mesoporous molecular sieve is selected from one or more of ZSM-5 molecular sieve, Y-type molecular sieve, beta molecular sieve, MCM-41 molecular sieve and SBA-15 molecular sieve.
3. The method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the mesoporous molecular sieve is prepared by sequentially carrying out acid treatment and alkali treatment on a molecular sieve.
4. The method for synthesizing p-methoxybenzaldehyde according to claim 3, characterized in that: the mole ratio of silicon oxide to aluminum oxide in the molecular sieve is 3-500: 1.
5. the method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the mesoporous molecular sieve is prepared by a method comprising the following steps: 1) Carrying out acid treatment on the molecular sieve by using an acid solution, and washing, drying and roasting to obtain the acid-treated molecular sieve; 2) And (3) carrying out alkali treatment on the molecular sieve subjected to acid treatment by adopting an alkali solution, and washing, drying and roasting to obtain the mesoporous molecular sieve.
6. The method for synthesizing p-methoxybenzaldehyde according to claim 5, characterized in that: in the step 1), the acid in the acid solution is selected from one or more of oxalic acid, boric acid, acetic acid, hydrochloric acid and propionic acid; and/or, in the step 2), the alkali in the alkali solution is selected from one or more of sodium hydroxide, sodium carbonate, organic amine and organic quaternary ammonium hydroxide.
7. The method for synthesizing p-methoxybenzaldehyde according to claim 6, wherein: the organic amine is selected from one or more of ethylenediamine, triethylamine, n-butylamine and piperidine; and/or, the organic quaternary ammonium base is selected from the group consisting of one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
8. The method for synthesizing p-methoxybenzaldehyde according to claim 5, characterized in that: in the step 1), the molar concentration of the acid solution is 0.05-5moL/L; and/or in the step 1), the temperature of the acid treatment is 30-180 ℃; and/or in the step 1), the acid treatment time is 0.5-48 h; and/or, in the step 2), the molar concentration of the alkali solution is 0.05-5moL/L; and/or in the step 2), the temperature of the alkali treatment is 30-180 ℃;
and/or, in the step 2), the time of the alkali treatment is 0.5-48 h.
9. The method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the catalyst is prepared by a method comprising the following steps: and carrying out ball milling and roasting on the active metal salt and the mesoporous molecular sieve to obtain the catalyst.
10. The method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the metal oxide is selected from one or more of zinc oxide, manganese oxide, magnesium oxide, barium oxide, calcium oxide, lithium oxide, sodium oxide, potassium oxide and rubidium oxide; and/or the mass of the metal oxide is 3-30% of the mass of the catalyst.
11. The method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the temperature of the methylation reaction is 80-250 ℃; and/or the pressure of the methylation reaction is 0.3-6MPa.
12. The method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the synthesis method comprises the following steps: 1) Mixing the p-hydroxybenzaldehyde, the dimethyl carbonate and a catalyst to obtain a reaction mixture; 2) And carrying out methylation reaction on the reaction mixture under inert atmosphere to obtain the p-methoxybenzaldehyde.
13. The method for synthesizing p-methoxybenzaldehyde according to claim 12, characterized in that: the mass ratio of the catalyst to the p-hydroxybenzaldehyde is 0.01-0.2: 1; and/or the molar ratio of the dimethyl carbonate to the p-hydroxybenzaldehyde is 1-10: 1.
14. the method for synthesizing p-methoxybenzaldehyde according to claim 1, characterized in that: the synthesis method comprises the following steps: 1) Filling the catalyst in a fixed bed reactor, and introducing inert gas into the fixed bed reactor to ensure that the pressure in the fixed bed reactor reaches the reaction pressure; 2) And heating the fixed bed reactor to a reaction temperature, and continuously introducing the p-hydroxybenzaldehyde and the dimethyl carbonate into the fixed bed reactor to perform methylation reaction to obtain the methoxybenzaldehyde.
15. The method for synthesizing p-methoxybenzaldehyde according to claim 14, wherein: the mol ratio of the dimethyl carbonate to the p-hydroxybenzaldehyde is 1-10: 1; and/or the quality of the p-hydroxybenzaldehydeThe volume space velocity is 0.2 to 10 hours -1 。
16. A catalyst as claimed in any one of claims 1 to 15.
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